CN102083749B - Method for separating nanomaterials - Google Patents
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- CN102083749B CN102083749B CN200980125621.XA CN200980125621A CN102083749B CN 102083749 B CN102083749 B CN 102083749B CN 200980125621 A CN200980125621 A CN 200980125621A CN 102083749 B CN102083749 B CN 102083749B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
- C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/02—Electrophoretic coating characterised by the process with inorganic material
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/66—Electroplating: Baths therefor from melts
- C25D3/665—Electroplating: Baths therefor from melts from ionic liquids
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/02—Electroplating of selected surface areas
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
Abstract
A method for dispersing nanomaterial comprising an electrochemical process, a solution of dispersed nanomaterial, comprising individual charged nanomaterial at a concentration of about O.1 mgm-1 or more and a solvent and an electrochemical cell are described.
Description
The present invention relates to for disperseing the method with separating nanomaterials particularly nanotube.Especially, the invention provides the method that wherein can use electrochemical process dispersion and separating nanomaterials.
Carbon nanotube is important material system, provides unique character, comprises the highest known thermal conductivity, the highest physical strength, large current density capacity and a series of important (light) characteristic electron.Except basic science is paid close attention to, nanotube is also proposed to be used for a large amount of application, scope from high performance composite to transparent conductor, solar cell and nano-electric devices (nanoelectronics), as Baughman, R.H., the science (Science) of A.A.Zakhidov and W.A.de Heer, described in 2002.297 (5582): the 787-792 pages.But, before nanotube is developed its whole potentiality, still have many critical obstacles to need to overcome.
Carbon nanotube can be divided into two classes: Single Walled Carbon Nanotube (SWNT) and multi-walled carbon nano-tubes (MWNT).SWNT is pure carbon tracheary element, and it can be considered to single " rolling " Graphene (graphene) sheet.The diameter of SWNT typically is about 1-1.5nm, and their character depends on the angle (chiral angle) that their diameter and they are rolled from graphene film.Multi-walled carbon nano-tubes is made up of some concentric SWNT layers.
The definition of nanotube can extend to those skilled in the art a large amount of variant of being familiar with and derivative, comprise the existence (room of such as defect, other ring as heptagon, and via the change of hydridization), built-in materials (endohedral material) (filling hollow core with other material), chemical functionalization, two (or many) gather and more complex topology structure.
When growing, nano-tube material is uneven, comprises the mixture of impurity and intrinsic different nanotube species.The electronics of carbon nanotube and optical property depend on their diameter and helicity (angle between graphite lattice and nanometer tubular axis).Thus, for SWNT, can (m, n) index be used to mark each species.As described in Meyyappan, M., 2005:CRC Press, in typical SWNT sample, about 1/3 is metallic and 2/3 is semiconductive.Although achieve progress in the materials synthesis of multiple material with type different from each other, pure (material) synthesis is still unknown so far.
In the future of material, the importance that can be separated two kinds of different SWNT should not be underestimated.Such as, semiconductive pipe must be used individually to prepare good field-effect transistor, and if want preparation example as the low electrical resistant material for transparent film, then must only there is metallic nanotubes (Kim, W.J. etc., materials chemistry (Chemistry of Materials), 2007.19 (7): the 1571-1576 pages).
It is therefore clear that before can using the photoelectric property of carbon nanotube with its whole potentiality, cheap and scalable be required by the method for characteristic electron separating nanotubes.In addition, most of nanotube sample by metal catalyst, support of the catalyst, or the amorphous of other type, nanoparticle or graphite carbon pollute.It is difficult for processing described material to obtain pure nanotube, typically comprise oxidation, ultrasonic, wash and filter multiple step, these steps are time-consuming, the inherent nature of infringement nanotube and usually modest efficacy.
The difficulty of abstraction and purification is associated with solvability or dispersiveness that problem widely, particularly nanotube have non-constant in conventional solvent system.Nanotube dispersion/solution that height requirement is good, to be introduced by nanotube in specific application, the nanotube coatings of such as depositing homogeneous, forms electrode assemblie and prepares high performance composite.
Typically use the dispersion of ultrasonic realization in low viscosity solution, high strength separating nanotubes aggregate wherein used is SWCNT bundle even.But this technology also can cause infringement.Only knownly in minority solvent (as NMP, DMA etc.), be in extremely low concentration (< 0.01mg/ml, about < 0.001 % by weight) the stabilising dispersions (Giordani of the independent nanotube that do not adulterate, S. the Physica Status Solidi B-Basic Solid State Physics waited, 2006.243 (13): the 3058-3062 pages).
In order to prevent reassociating, usually polymkeric substance or tensio-active agent is added to solution, in the nanotube surface that described polymkeric substance or tensio-active agent can be adsorbed onto exposure or become (the Shaffer of grafting due to chain rupture, M. etc., Editor S Advani.2006, World Scientific. 1-59 page).Be dissolved in the amphiphilic polymer in water, especially effectively as poly-(hydroxy amino ethers) (PHAE), poly-(vinyl alcohol) (PVA) and PVA/ PVP (PVP) have been proven, although also studied the organic system based on polystyrene (PS), ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) and polypropylene (PP).Employed a series of tensio-active agent, the most common is SDS, SDBS and biliary salts.
These non-covalent strategies moderately come into force when lower concentration, but all need strong sonication, and contaminated samples inherently.Except independent nanotube or replace independent nanotube, typically leave nanotube bundle, it only can be removed by ultracentrifugation.
With polymkeric substance or the direct covalent chemical of charged functional groups is functionalized is also used, but it damages the inherent nature of nanotube especially.
The method of the nanotube that most promising dissolving is independent depends on and chemically makes nanotube charged under rodent Redox Condition, or in peracid protonated (Ramesh, S., Deng, Journal of Physical Chemistry B, 2004.108 (26): the 8794-8798 pages), or in DMF, use sodium naphthalene (sodium napthalide) reduction (Penicaud, A., Deng, Journal of the American Chemical Society, 2005.127 (1): the 8-9 pages).
Current, there are many successfully technology that obtains in various degree they to be separated for the electronic property by nanotube.All need to prepare independent nanotube (being generally SWNT), as prerequisite by ultrasonic and ultracentrifugation.Dielectrophoresis based on metallicity and the polarizability of semiconductive SWNT difference and they are separated (Krupke, R. etc., Science, 2003.301 (5631): the 344-347 pages).It is reported that described method only produces 80% enrichment, and be limited to the high cost of microelectrode, very little sample size and the problem relevant to preparing better quality initial soln.
Density gradient ultracentrifugation may be used for the difference utilizing buoyant density, the carbon nanotube of small quantity is pressed their diameter and electronic type classification (Arnold, M.S. etc., Nature Nanotechnology, 2006.1 (1): the 60-65 pages).But required ultracentrifugation Multiple Cycle (multiple cycles) hinders the commercial viability of this technique due to the nature of its costliness.
Simpler method is with dispersion and centrifugal be combined as basis, general employing amine aqueous solution (Maeda, Y. etc., Journal of the American Chemical Society, 2005.127 (29): the 10287-10290 pages), but only produce the enrichment of appropriateness but not be separated completely.
Anion-exchange chromatography is for separating of the SWNT be wrapped in DNA (Zheng, M. and E.D.Semke, Journal of the American Chemical Society, 2007.129 (19): the 6084 pages of tops).Although this technology is of value to a small amount of nanotube be separated of preparation, this method is subject to strictly limiting for the high cost of the DNA in packing technology and anion-exchange chromatography.Needing fully to remove DNA for many potential application is another one shortcoming.
Also various chemical technology is developed for separating of SWNT.Peng, X. etc., Nature Nanotechnology, describes use biporphin in 2007.2 (6): the 361-365 pages or ' nano-tweezers (nano tweezers) ' is separated the SWNT of different helicity.Kim, W.J. etc., Chemistry of Materials, is described in 2007.19 (7): the 1571-1576 pages and uses diazonium salt functionalize metal's property nanotube selectively, they be separated thereafter by electrophoretic method.As Banerjee, S. etc., Nano Letters, described in 2004.4 (8): the 1445-1450 pages, ozone decomposed also may be used for by diameter separating nanotubes.Wunderlich, D. etc. are described in the alkylation functionalize metal's property nanotube selectively in liquefied ammonia in the Journal of Materials Chemistry of 2008.
Although some in these technology are more effective than other, they comprise batch treatment, considerably less amount and by functionalized and destroy the structure of nanotube inherently.
Therefore, obviously need the simple effective method that can carry out in a continuous manner for separating of nano material, and described method is not by the puzzlement of above-mentioned shortcoming.
Thus, the present inventor found surprisingly by use electrochemical process can realize nano material particularly nanotube effective dissolving be separated.
Up to the present, the prevailing electrochemical applications of nanotube be as at electrochemical appliance as the noble electrode in electrical condenser and fuel cell or as microelectrode.In these backgrounds, the redox characteristic of nanotube is out in the cold.As Kavan, L. wait at Journal of Physical Chemistry B, described in 2001.105 (44): the 10764-10771 pages, have studied the redox electrochemistry of the nanotube attaching to solid carrier before this, but never use it for the object of dissolving or being separated.On the other hand, well-known redox purifying is used for atomic species, and be used in large scale industry process, such as the purifying of copper, as described in the Industrial Electrochemistry.1993:Blackie Academic and Professional of Pletcher, D. and D.Walsh.Redox electrochemical applications in purifying discrete nano-material be surprising progress.
First aspect, the invention provides the method for dispersing nanometer material, and described method comprises electrochemical process.Advantageously, have been found that when adopting such process, can while avoiding that infringement is produced to nano material dispersing nanometer material effectively.Especially, the invention provides scalable, cheap and potential continuous print method is for separating of a large amount of nano material.
In addition, by controlling to carry out the condition of electrochemical process, can dispersing nanometer material selectively.Such as, when nano material comprises nanotube, by controlling the condition of carrying out electrochemical process, can disperse that there is nanotube of different nature selectively.Thus, can based on their characteristic electron separating nanotubes, such as semiconducting nanotubes is separated by size or by helicity with metallic nanotubes.
Further, the invention provides the solution of the nano material of dispersion, described solution comprises concentration for about 0.1mgml
-1above independent nano material and solvent.The independent nano material of the dispersion of high density is suitable for further operating.Before making the present invention, also can not when do not need to use extra tensio-active agent, surface-modifying agent, chemical functionalization or protonated obtain the solution with such highly concentrated nano material.
In one embodiment, the invention provides the solution of the nanotube of dispersion, described solution comprises concentration for about 0.1mgml
-1above independent charged nanotubes and solvent.
Further, the invention provides electrochemical cell, described electrochemical cell comprises working electrode, multiplely comprises electrolytic solution to electrode, and wherein said working electrode comprises nano material.Preferably, during use, multiple be different to each in electrode and the electromotive force between working electrode.
In the method for the invention, by electrochemical process dispersing nanometer material.
As used in this article, term " nano material " refers to have at least at the material that a direction is the morphological specificity of less than about 0.1 μm.Therefore, nanotube, nanofiber and nanoparticle contained in this term.
In some embodiments, nano material is the molectron of nanotube, nanofiber and/or nanoparticle.The molectron that method of the present invention allows dispersion such.
Term " nanoparticle " is for representing the particle with discrete crystal structure, and it can be electrochemically oxidized as a whole or reduce and not make the inherent atomic structure of particle degenerate.The example of suitable nanoparticle comprises and comprises precious metal such as, as, the nanoparticle of platinum or gold.
Term " nanofiber " is for representing that diameter is the fiber of less than about 0.1 μm.
In some embodiments, nano material comprises nanotube or nanofiber.Preferably, nano material comprises nanotube.Preferred nano material comprises carbon nanotube.
In one embodiment, can by carbon nanotube boron and/or N doping, to regulate the electroconductibility of carbon nanotube.Typically concentration of dopant will be about 1 atom %, but can be higher or lower significantly.
Nanotube for the inventive method can be SWNT or MWNT, preferred SWNT.Preferably, nanotube is carbon nanotube.Nanotube can have diameter within the specific limits.Typically, for SWNT, nanotube will have about 0.4 to the diameter within the scope of about 3nm.When nanotube is MWNT, diameter by preferred in about 1.4 scopes to about 100nm.Preferably, carbon nanotube is SWNT.Suitable nanotube can be purchased certainly, such as, and SWeNT, Carbon Nanotechnologies, Inc., Carbolex, Inc. and Thomas Swan Ltd.
Although detailed content following is herein concentrated on the nanotube, method of the present invention is applicable to other can need the nano material of selective separation by size or composition control oxidation-reduction potential.The redox active particle of low intrinsic conduction may need load on porous, electrically conductive skeleton.
As used in this article, term " electrochemical process " refers to the process that chemical reaction wherein occurs in the interface of electronic conductor (electrode) and ionophore (electrolytic solution), or relates to the process that charged species moves between electrode and electrolytic solution.
In one embodiment, method of the present invention is included in working electrode and applies electromotive force between electrode, and wherein said working electrode comprises nano material, as nanotube, and working electrode and the part to electrode formation electrochemical cell, described electrochemical cell also comprises electrolytic solution.
As used in this article, term " working electrode " refers to the electrode that interested electrochemical process occurs in its interface.
Nano material is comprised for the working electrode in the inventive method.In one embodiment, working electrode can be made up of nano material substantially, and namely electrode is containing affecting in fact other component of electrode performance.Favourable for the purity that some reasons are such.First it allows to disperse to receive in a large number material by a simple process, and described process can easily control.Secondly, it makes to become direct to the monitoring of course end because its by with dissolution degree needed for working electrode for mark.3rd, system keeps not having undesired additional contaminants.
The electrode comprising nano material is well known in the art.Such as, as the J.Phys Chem B of 2004, described in 108 (52) 19960-19966, use " Buckie paper (bucky paper) " or other Thin Film Carbon Nanotube electrode as the noble electrode in electrochemical cell before." Buckie paper " can be purchased from Nanolab, Inc., MA, USA.The routine techniques preparation that the electrode comprising nano material can be familiar with by those skilled in the art.Such as, such electrode can be prepared by the solution filtering/disperse containing nano material, as the Composites Part A:Applied Science and Manufacturing at Wang etc., described in (35) 10,1225-1232 (2004).
The fundamental principle of electrochemical techniques of the present invention be comprise nano material working electrode and to electrode between apply relatively large electromotive force, until nano material to become fully highland charged and spontaneously dissolve.This process can use large positive voltage to remove electronics (oxidation) from nano material, the solution of generating strap positive electricity nano material, or use large negative voltage to increase electronics (reduction) to nano material, the solution of electronegative nano material is provided.
When working electrode comprises nanotube, preferably apply large negative potential so that reduced nano pipe.Reduction is preferred, because more easily obtain required electromotive force in standard solvent window (standard solvent window), and gained carbon nanotube ionic (carbon nanotubide ion) easier solvation.When reduced nano pipe, working electrode is negative electrode and is anode to electrode.
As mentioned above, in the method for the invention, working electrode and to electrode between apply large electromotive force.Can depend on that the ionization energy of nano material regulates and be applied to working electrode and to the electromotive force between electrode.When applying negative potential, the applying electromotive force preferably measured relative to standard hydrogen electrode is the electromotive force of about-0.6V or more negative, the electromotive force of about-0.8V or more negative, the preferably electromotive force of about-1.0V or more negative, the preferably electromotive force of about-1.5V or more negative, the preferably electromotive force of about-2.0V or more negative, the preferably electromotive force of about-2.5V or more negative.Preferably relative to standard hydrogen electrode measure applying electromotive force in about-1 scope to about-2V.
When applying positive potential, the applying electromotive force preferably measured relative to standard hydrogen electrode is about more than 1.0V, preferably about more than 1.1V, preferably about more than 1.2V, preferably about more than 1.3V, preferably about more than 1.5V.The applying voltage preferably measured relative to standard hydrogen electrode is about below 3V, about below 2.5V, about below 2.0V.
Steady state current is associated with the dissolution rate of nano material, and can maximize by regulating the electromotive force of the composition of electrolytic solution and the surface-area of working electrode and applying.
Working electrode and to electrode between apply electromotive force time except by may need the working electrode consumption supplemented limit except be not particularly limited.In one embodiment, the time applying electromotive force can in the scope of about 1 to about 16 hour.
Specifically do not limit the size of working electrode.In some embodiments, working electrode can have about 0.2 to about 1.0cm
2surface-area in scope.In other embodiments, surface-area can be larger significantly, when particularly implementing described method with commercial size.
Electrolytic solution of the present invention is the electrolytic solution making charged nanosize material settling out.Electrolytic solution can be formed in an electrochemical cell in situ by being added in solvent by suitable salt.Can use for the standard of dry organic electrolyte system, wide stability salt, comprise sodium tetraphenylborate, hexafluorophosphate and lithium perchlorate.
Those skilled in the art will be familiar with suitable solvent.Especially, preferred polarity, non-proton dry solvent.The suitable solvent for charged nanosize material includes but not limited to the dimethyl formamide (DMF) of dry (anhydrous) and anaerobic, N,N-DIMETHYLACETAMIDE (DMA) and N-Methyl pyrrolidone (NMP).
Alternatively, the ionogen based on nano material can be used, as the ionogen based on nanotube, such as, basic metal nanotube salt that is that prepared by direct reaction dystopy (ex situ) or that prepared by interpolation basic metal original position.
In one embodiment, can by making commercially available nanotube and comprising that the electric liquid of metal with amine solvent (electronic liquid) contacts and ionogen based on nanotube is prepared on dystopy ground.
Term " electric liquid " in this article for represent when when there is no chemical reaction by metal as alkaline-earth metal or basic metal, such as, when sodium is dissolved in polar solvent formed liquid, the prototypic example of described polar solvent is ammonia.Electronics is discharged in solvent and forms high reducing solution by this process.When being reluctant bound by theory, these solution dissolve nanotube based on two factors.First, the electronics of carbon species means that they form electronegative negatively charged ion.Secondly, these electronegative negatively charged ion are stably disperseed due to electrostatic repulsion.
The metal used is dissolved in amine the metal forming electric liquid.Those skilled in the art will be familiar with suitable metal.Preferably, described metal is selected from the group be made up of alkali and alkaline earth metal ions.Preferably, metal is basic metal, particularly, and lithium, sodium or potassium.Preferable alloy is sodium.
The amount of the metal that careful control comprises in the solution is favourable.Too many metal is present in electric liquid and eliminates the charged possibility of (being saturated) selectivity, and prevents Nanotube dispersion from forming ionogen based on nanotube due to the electrostatic repulsion between shielding carbon species.Therefore, the amount that preferable alloy exists makes the ratio of the carbon atom in the carbon nanotube that in electric liquid, atoms metal contacts with electric liquid be about less than 1: 4, and preferably about less than 1: 6, preferred about less than 1: 8, preferably about less than 1: 10, preferably about less than 1: 15, preferably about less than 1: 20.In some embodiments, the amount that metal exists makes the proportional range of the carbon atom in the carbon nanotube that in electric liquid, atoms metal contacts with electric liquid be about 1: 3 to about 1: 10, and about 1: 3 to about 1: 8, about 1: 3 to about 1: 6, about 1: 3 to about 1: 5, preferably about 1: 4.Carbonatoms in nanotube can by those skilled in the art the simple computation be familiar with determine.
By dissolving metal is formed electric liquid in amine solvent.In some embodiments, amine solvent can be C
1to C
12amine, C
1to C
10amine, C
1to C
8amine, C
1to C
6amine, C
1to C
4amine.Amine solvent is preferably selected from ammonia, methylamine or ethamine.Preferably, amine solvent is ammonia.In one embodiment, metal is sodium and amine solvent is ammonia.
Preferably by guaranteeing all material all dry and anaerobic, air and moisture are got rid of from system.In principle, the pollutent of lower concentration can be removed by electrochemical reaction, but preferably remove pollutent in advance.
In the method for the invention, by working electrode and to electrode between apply electromotive force from working electrode dissolve nano material.Electrochemical cell can comprise multiple to electrode.Specifically restriction be used in the inventive method to electrode, but preferably it is electrochemicaUy inert under the applied conditions.Thus, those skilled in the art are suitable to electrode by being familiar with.Suitable comprises vitreous carbon, graphite, platinum and nanotube paper to the example of electrode.
In one embodiment, electrochemical cell can also comprise reference electrode or false reference electrode (pseudo reference electode).This interpolation is favourable, because it allows maximum control, particularly in small-scale experiment.For in the solvent/electrolyte system in the inventive method, standard reference electrode (its major part is usually designed for aqueous systems or comprises aqueous systems) is not always easy to obtain, so can use false reference electrode, as platinum filament.Some reference electrode systems are as Ag/AgNO
3be suitable for too.
In one embodiment of the invention, by working electrode with electrode is arranged in the compartment separated that is connected by suitable electrochemical membrane or spacer.Suitable electrochemical membrane and spacer comprise porous material, such as fluorinated polymer films, and glass or other inert fiber pad.In such setting, electrolytic salt or to electrode materials to electrode place oxidized (or reduction), to balance the reduction (or oxidation) of nano material at working electrode place.The solution of nano material that is charged, dispersion can be collected from working electrode compartment.When carrying out this process in a continuous manner, may be necessary to increase ionogen or the further interpolation to electrode materials.
In alternate embodiment, working electrode and electrode is contained in a compartment.In such setting, nano material is dissolved from working electrode and is deposited to one or more to electrode subsequently.Described process can continue until the nano material be provided in working electrode exhausts, or until the selected portion being provided in the nano material in working electrode exhausts.By the weight of the monitoring electrode when electrochemical reaction is carried out or integrating electric measurement in time can be passed through by the total charge of electrochemical cell, determine the ratio of the nano material of having dissolved from working electrode.Can such as by means of mechanical means prepare powder or by further electro-chemical machining prepare dispersion and to electrode collect deposition nano material.
Preferably, the electrochemical cell be used in the present invention be configured such that working electrode and one or more electrode be contained in same compartment.
As mentioned above, nano material such as nanotube is uneven, and each component has different oxidation-reduction potentials, as the Physical Review B at Okazaki, K. etc., and 2003, described in 68 (3).Therefore, in the method for the invention, by selecting the electromotive force of working electrode, the different piece containing nano-tube material can be dissolved.Thus the invention provides abstraction and purification nano material particularly containing the mechanism of nano-tube material.This selectivity can realize in one of two ways.In one embodiment, abstraction and purification can be realized by the dissolving controlled containing nano material working electrode.This can by controlling be applied to working electrode and complete the electromotive force between electrode.Such as, nanoparticle carbon ribbon electricity first can be made then to be dissolved away, leave (purifying) nanotube working electrode of enrichment.Similarly, the order of the applying electromotive force step that can optionally increase gradually with size, dissolves respectively by nanotube that is metallic or diameter dependent form semiconductive.When the dissolving by controlling working electrode realizing being separated, being preferably applied to working electrode and being enough to dissolve the nano material at least about 1%, at least about 5%, at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, at least about 98%, at least about 99% of working electrode to electromotive force between electrode.In this embodiment, the product obtained is the solution of dispersion, independent charged nanosize material, described nano material optionally through regulating the dissolving being applied to working electrode and the electromotive force between electrode being contained to nano material working electrode with control, and is separated by size, helicity and/or characteristic electron.
In an alternate embodiment, the abstraction and purification of nano material can realize the deposition on electrode by controlling to have dissolved nano material.In this embodiment, preferably, working electrode and to electrode between apply enough large electromotive force to dissolve the nano material at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, at least about 98%, about 100% of working electrode.Electrochemical cell can comprise multiple to electrode, and makes at working electrode different to the electromotive force between electrode with every next one.The difference of the oxidation-reduction potential of charged species is different from electrode by causing them to be deposited on selectively, thus allows nano material from comprising its working electrode abstraction and purification.Preferably, according to and the distance of working electrode arrange electrode in the mode at interval in order, thus the species of dissolving are sequentially moved from minimum potential to maximum electrical potential.This set to allow when reaching electromotive force needed for deposition pure species in each deposition to electrode place.
The present invention thus provide scalable, cheap with potential continuous print method for separating of a large amount of nano materials.The purified nanotubes material prepared by the inventive method can be directly applied to as solar cell, transistor and sensory field.Especially, nano material dispersion may be used for multiple object, comprises the separation of coating, matrix material, and the Reactive Synthesis functionalized nanotube of exploitation for making nanotube charged by chemical means.
The method of the application of the invention, the solution of that can obtain dispersion, independent charged nanosize material.
When working electrode comprises nanotube, the product of the inventive method can be the solution of dispersion, charged independent nanotube.Those skilled in the art will be familiar with may be used for determining the technology that (separating (debundled) of bundle) nanotube of individuation exists.The example of appropriate technology is small-angle neutron scattering (SANS), as the J Phys Chem B. of J.A.Fagan etc., (2006), and 110, described in 23801.
SANS is the effective technology for detecting SWNT structure in solution.More specifically, SANS may be used for determining that SWNT is as the existence of isolated species or with bundle or bunch existence.SANS provides the structural information of macroparticle in solution (in the scope of 1 to 1000nm).SANS intensity I (Q) is and Q
-Dproportional, wherein D is the fractal dimension (fractal dimension) of nanotube.Thus, be Q for the SANS pattern desired by fully decentralized rod-shaped objects (i.e. D ≈ 1)
-1pattern.In addition, non-monodispersed SWNT, be namely made up of aggregate or the network of rod those, show larger fractal dimension, typically from 2 to 4.
Found out that, when applying the method according to the invention, the concentration of astonishing high nano material particularly nanotube can be obtained.More specifically, it is believed that before making the present invention, when there is no surface-modifying agent chemical functionalization or protonated, owing to reaching thermal equilibrium, the maximum concentration of the independent nanotube that can obtain in the solution is 0.01mgml
-1.But the present inventor has obtained higher than about 0.01mgml
-1concentration.In some embodiments, the concentration of independent nanotube is about 0.1mgml
-1above, about 0.5mgml
-1above, about 1mgml
-1above, about 5mgml
-1above, about 10mgml
-1above, about 50mgml
-1above, about 100mgml
-1above.
Further advantage related to the present invention can obtain selectivity by the condition controlling to carry out electrochemical process.More specifically, to be that metallic carbon nanotubes has precedence over semiconducting nanotubes charged for the characteristic of the method.Described effect depends on the variable electronic affinity of type, diameter and helicity owing to SWNT.
The type of the nanotube existed in solution can be determined by Raman scattering techniques (the Physics Reports (2005) of Desselhaus etc., 40A).Raman scattering is the effective technology of the particular type for determining to be present in the SWNT in the sample that is made up of mixing nanotube.Raman scattering is that sample is via the inelastic optical scattering process had from the power loss of vibronic modes (phonon) or the central electron of gain.Because only there is the scattering (1/10 in this way of very small amount of phonon
7) time, so Raman spectroscopy typically uses laser as the homogeneous beam of high strength.
SWNT is the graphite flake rolled, and due to the characteristic of this tubulose, its electronics is limited in the radial direction of nanotube.This quantization causes large spike (spikes) in their density of electronic states (electronic Density of States (eDOS)), is called van hove singularity (van Hove singularities).If incident light mates these sharp peak-to-peak differences, then Raman scattering is resonance.Thus arranged by specific nanotube at the Raman spectrum at any setted wavelength place, described specific nanotube has the transition of this wavelength of coupling in their eDOS.In order to predict the nanotube with photoresonance, often use Kataura figure.This figure is the transition that the calculates different SWNT figure as the function of their diameters.
Lower than 400cm
-1time, the Raman spectrum of SWNT is by radial breathing modes (Radial Breathing Mode) (RBM) domination.The energy of this phonon and the diameter of SWNT are inversely proportional to.The Raman spectrum of the blend sample of nanotube by display from all RBM peak and, described RBM is from the SWNT with photoresonance.Therefore, when learning optical maser wavelength, which kind of nanotube can be read from Kataura figure and being present in given sample.If get SWNT sample and carry out chemical treatment to it, then compare its Raman spectrum and the Raman spectrum of untreated nanotube, then the relative populations of RBM increases or reduces the relative increase of particular type SWNT or the strong evidence of minimizing in sampling.In addition, as seen from Fig., for given energy, from the transition typically good separation of metallic nanotubes and semiconducting nanotubes.Therefore, typically, spectrum comprises the region of the clear enough at the peak corresponding with metallicity SWNT and semiconductive SWNT.Therefore determining that based on characteristic electron in SWNT separation degree, Raman spectroscopy is effective technology (the Physics Reports (2005) 40 of Dresselhaus M.S. etc.).
After preparing the dispersion of independent nano material, preferably nanotube, other step more than one can be carried out, so that further separating nanomaterials, such as, based on characteristic electron, size and/or helicity.
In one embodiment, can make electric charge quencher and being separated further by one or more dispersing materials gradually by using suitable quencher, described quencher includes but not limited to O
2, H
2o, I
2, proton-organic solvent and alcohol (or other proton species).Along with adding quencher, first the species with highest energy electronics will deposit.By adding suitable stoichiometry, required part can be separated.Such as, with the part of the total charge postprecipitation of predetermined amount in can being collected in.
Alternatively or except chemical quencs, can make electrochemically.In the case, increase electric charge (addition charge) on nanotube-Ji negatively charged ion is removed by applying little voltage to (in other respects inertia) electrode being placed in nanotube dispersion.By the electromotive force of control electrode, the nanotube with different electron affinity can be oxidized and be deposited on electrode.The electrode of working electrode (or series) is made to remain on fixing electromotive force in permanent electromotive force mode; Can also will preferably be arranged in the compartment of still ionic connection at a distance to electrode, alkalimetal ion be reduced at described compartment and reclaims.The electromotive force that reference electrode accurately controls at working electrode place can be used.
Alternatively, or in a further step, solvent (electrolytic solution) can be removed gradually, first at most charged/minimum species are deposited.These two kinds of mechanism allow, such as on the one hand by nanotube length, to press nanotube characteristic electron (semi-conductor band gap) on the other hand and be separated.
Optionally, quencher includes but not limited to RI, and wherein R is alkyl, may be used for chemical modification carbon species.By reacting in the dispersion of independent nanotube, on can realizing ideal in nanotube surface uniformly functionalized (typically functionalized only occur on the surface of nanotube bundle).
Optionally, the solution of (being separated in advance) carbon species can be gone lentamente to stablize (by quencher or removal solvent) to make carbon species crystallization.
Optionally, when nano material comprises nanotube, can be separated further according to size by the nanotube of chromatography by part classifying, independent dispersion in a dry environment.
Optionally, charged nanotube can be transferred in the organic solvent of other drying, as dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMA) and N-Methyl pyrrolidone (NMP), for further process.
The following drawings and embodiment will describe the present invention further by reference, described drawings and Examples never mean and limit the scope of the invention.
Accompanying drawing explanation
Figure 1A and 1B is two kinds of different sketch maps arranged of the electrochemical cell that may be used in the inventive method;
Fig. 2 is presented at the Raman spectrum of CoMoCAT SWNT before and after application the inventive method.
In figure ia, the working electrode (2) and the reference electrode (4) that comprise nano material are placed in a compartment (8), be placed in compartment (10) separately electrode (6), the described compartment (10) separated is connected to first compartment by electrochemical membrane (12) simultaneously.When working electrode and to electrode between apply electromotive force time, nano material (14) is distributed in electrolytic solution (16).
In fig. ib, working electrode (18) and a series of electrode (20) to be arranged in same compartment (22).When working electrode and to electrode between apply electromotive force time, depositing nano-materials is on electrode.
Embodiment
In this embodiment, use and comprise following electrochemical cell: Buckie paper working electrode, high-sequential pyrolytic graphite to electrode, the false reference electrode of platinum, and sodium tetraphenylborate in DMF as electrolytic solution.Electrochemical cell is remained on negative potential to make SWNT be reduced, repel each other, to overcome the Van der Waals force making them keep together, and thus using Buckie paper as independent Nanotube dispersion in the electrolytic solution.Then using reduction nanotube deposition on electrode as carbon nano-tube film.
Electrochemical cell is prepared and is operated as follows.The sodium tetraphenylborate of 10mg is added to and accommodates in clean, the dry 25ml 3 neck round-bottomed flask of 6mm glass shell magnetic stirring bar.Utilize Shi Lanke line (Schlenk line) technology of standard, under 3 times flask being placed in nitrogen atmosphere by suction filling, use heat rifle heating flask and content simultaneously.After flask cooling, under a nitrogen the pre-dried DMF of 7ml to be transferred in flask and by solution stirring 2 minutes.
A slice 6cm × 8cm Buckie paper is attached to a platinum filament, described Buckie paper be by with ultrasonic by Nanotube dispersion in dichlorobenzene, then under reduced pressure ready-made by 0.2 μm of PTFR membrane filtration.
This Buckie paper working electrode is inserted by Soviet Union's bar sealing member (subaseal), uses heating gun dry, and in maintenance battery while positive pressure of nitrogen, be inserted in reaction vessel.This working electrode is reduced, thus when electrolytic solution does not directly contact platinum filament by Buckie paper partial immersion in electrolytic solution.
By be attached to platinum filament be made up of a slice 5mm × 9mm high-sequential pyrolytic graphite the second Soviet Union be inserted into electrode cling in sealing member; Contiguous insertion platinum filament serves as reference electrode.Use heating gun all to be heated by two electrodes, and subsequently they are inserted in the remaining side arm of flask.Then two electrodes are immersed in electrolytic solution.Then whole electrode is all attached to the respective electrode folder of potentiostat, to avoid shorted contacts.The battery diagram completed in figure ia.
While stirring, battery is kept 30 minutes at-2V.During this period, see that nanotube flows to electrolytic solution from Buckie paper working electrode and produce grey solution.Some in these nanotubes deposit to on electrode and remaining keep in the solution.
First specific nanotube reduces the easness that then deposits and depends on their characteristic electron.As shown in Figure 2, use Raman spectroscopy to demonstrate as expected, metallic nanotubes is the most easily reduced and first deposits from solution.When being reluctant bound by theory, a kind of explanation is this performance with available not occupy molecular state relevant close to fermi level, and the fermi level of known gold metallic nanotubes is inherently in lower energy.
Claims (43)
1. the method for dispersing nanometer material, described nano material is the molectron of nanotube, nanofiber and/or nanoparticle, described method comprises electrochemical process to obtain dispersion, independent charged nanosize material, and not by functionalized and destroy the structure of nanotube inherently;
Wherein said electrochemical process is included in working electrode and applies electromotive force between electrode, wherein said working electrode comprises described nano material, and described working electrode and described part electrode being formed to electrochemical cell, described electrochemical cell also comprises electrolytic solution.
2. method according to claim 1, wherein said nano material comprises nanotube.
3. method according to claim 2, wherein said nanotube is carbon nanotube.
4. according to the method in any one of claims 1 to 3, wherein described working electrode and described to electrode between apply positive potential.
5. method according to claim 4, wherein applied positive potential is more than 1V.
6. according to the method in any one of claims 1 to 3, wherein described working electrode and described to electrode between apply negative potential.
7. method according to claim 6, wherein applied negative potential is the electromotive force of-1V or more negative.
8. according to the method in any one of claims 1 to 3, wherein form described electrolytic solution by being added in solvent by salt.
9. method according to claim 8, wherein said electrolytic solution is dry polar aprotic solvent.
10. method according to claim 9, wherein said solvent is selected from the group be made up of dry and DMF, DMA and NMP of anaerobic.
11. methods according to claim 8, wherein said salt is selected from the group be made up of sodium tetraphenylborate, hexafluorophosphate and lithium perchlorate.
12. according to the method in any one of claims 1 to 3, and wherein electrolytic solution is the electrolytic solution based on nanotube.
13. methods according to claim 12, wherein said electrolytic solution is basic metal nanotube salt.
14. methods according to any one of claims 1 to 3,5,7,9 to 11 and 13, wherein said process is carried out in anaerobic water-less environment.
15. methods according to any one of claims 1 to 3,5,7,9 to 11 and 13, wherein said electrochemical cell also comprises reference electrode.
16. methods according to any one of claims 1 to 3,5,7,9 to 11 and 13, wherein said electrochemical cell comprises multiple to electrode, and described working electrode and each to electrode between apply different electromotive forces.
17. methods according to any one of claims 1 to 3,5,7,9 to 11 and 13, wherein said working electrode and electrode is contained in single compartment.
18. methods according to any one of claims 1 to 3,5,7,9 to 11 and 13, wherein said working electrode to be contained in the first compartment and to be describedly contained in the second compartment to electrode, and wherein said first and second compartments are connected by electrochemical membrane.
19. methods according to any one of claims 1 to 3,5,7,9 to 11 and 13, wherein by controlling to be applied to described working electrode and to disperse described nano material selectively to the electromotive force between electrode.
20. methods according to claim 19, wherein disperse described nano material selectively according to characteristic electron.
21. methods according to claim 19, wherein disperse described nano material selectively according to size.
22. methods according to claim 19, wherein disperse described nano material selectively according to helicity.
23. methods according to any one of claims 1 to 3,5,7,9 to 11,13 and 20 to 22, described method also comprises the step of the nano material being separated described dispersion.
24. methods according to claim 23, are wherein separated the material of described dispersion according to characteristic electron.
25. methods according to claim 23, are wherein separated the nano material of described dispersion by the selective electrochemical deposition on one or more electrode.
26. methods according to claim 24, wherein by controlling to be applied to described working electrode and described material electromotive force between electrode being separated to described dispersion.
27. methods according to claim 23, the nano material of wherein disperseing according to apart.
28. methods according to claim 27, are wherein separated the nano material of described dispersion by chromatographic technique.
29. methods according to claim 23, are wherein separated the nano material of described dispersion according to helicity.
30. methods according to claim 23, wherein by the quencher selectively of the nano material of described dispersion.
31. methods according to claim 30, wherein by the nano material chemical quencs of described dispersion.
32. methods according to claim 23, wherein by the nano material electrochemistry quencher of described dispersion.
The solution of the nano material of 33. dispersions, described solution comprises independent charged nanosize material and solvent, and the concentration of described nano material is 0.1mgml
-1above, wherein said nano material is the molectron of nanotube, nanofiber and/or nanoparticle, and wherein the structure of nanotube is not destroyed inherently by functionalized.
34. solution according to claim 33, wherein said nano material comprises nanotube, and described solution comprises independent charged nanotubes and solvent, and the concentration of described nanotube is greater than 0.01mgml
-1.
35. solution according to claim 34, it is 0.1mgml that wherein said solution comprises concentration
-1above independent charged nanotubes.
36. according to claim 34 or solution according to claim 35, and wherein said nanotube is carbon nanotube.
37. solution according to claim 36, wherein said nanotube is single-walled nanotube.
38. solution according to any one of claim 33 to 35 and 37, wherein said solvent is NMP or DMF.
39. electrochemical process are used for the purposes of dispersing nanometer material, wherein said nano material is the molectron of nanotube, nanofiber and/or nanoparticle, wherein the structure of nanotube is not destroyed inherently by functionalized, wherein said electrochemical process is included in working electrode and applies electromotive force between electrode, wherein said working electrode comprises described nano material, and described working electrode and described part electrode being formed to electrochemical cell, described electrochemical cell also comprises electrolytic solution.
40. 1 kinds of electrochemical cells, described electrochemical cell comprises working electrode, multiplely comprises electrolytic solution to electrode, wherein said working electrode comprises nano material, wherein said nano material is the molectron of nanotube, nanofiber and/or nanoparticle, wherein said electrochemical cell can disperse described nano material to obtain dispersion, independent charged nanosize material, and not by functionalized and destroy the structure of nanotube inherently.
41. electrochemical cells according to claim 40, wherein, in use, described multiple be different to each in electrode and the electromotive force between described working electrode.
42. according to claim 40 or electrochemical cell according to claim 41, wherein said working electrode and being contained in single compartment electrode.
43. according to claim 40 or electrochemical cell according to claim 41, and wherein said working electrode is contained in the first compartment, and is describedly contained in the second compartment to electrode, and wherein said first and second compartments are connected by electrochemical membrane.
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| EP2307313B1 (en) | 2008-07-03 | 2017-09-13 | UCL Business PLC | Method for dispersing and separating nanotubes |
| GB201104096D0 (en) * | 2011-03-10 | 2011-04-27 | Univ Manchester | Production of graphene |
| GB201105407D0 (en) * | 2011-03-30 | 2011-05-11 | Ucl Business Plc | Purification method |
| CN102320592A (en) * | 2011-08-26 | 2012-01-18 | 复旦大学 | Method for separating carbon nanotubes with different conductive performances |
| EP3402598A4 (en) | 2016-01-13 | 2019-08-21 | William Fitzhugh | Methods and systems for separating carbon nanotubes |
| US11383983B2 (en) * | 2017-10-10 | 2022-07-12 | Nec Corporation | Nanocarbon separation device, nanocarbon separation method, nanocarbon recovery method |
| JP6852801B2 (en) * | 2017-10-10 | 2021-03-31 | 日本電気株式会社 | Nanocarbon separator, nanocarbon separation method, nanocarbon recovery method |
| KR102296102B1 (en) * | 2019-12-11 | 2021-09-01 | 한국기계연구원 | Sustainably power-generating fuel cell using sea water |
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